Nitrobenzeneazo-n-difluoroalkyl-n-hydroxyalkylaniline dye compounds



Patented Oct. 21, 1952 UNITED STATES NITRQBENZENEAZO- N -DIFLUOROALKYL- N-HYDROXYALKYLANILIN E DYE COM- POUNDS Joseph B. Dickey, Kingspcrt, Tenn., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application May 23, 1951, Serial No. 227,93l

6 Claims.

This invention relates to new azo compounds containing a difluoroalhylamino group and their application to the art of dyeing or coloring textile materials made of or containing a cellulose alkyl carboxylic acid ester havin two to four carbon atoms in the acid groups thereof.

It is known to prepare azo dyes containing a CFa group. However, so far as I am aware, in every instance the CFs group is directly attached to an aryl group. By contrast, the fluoroalkyl group present in the compounds of my invention is (1) joined to a benzene nucleus through an amino group rather than directly, (2) contains two rather than three fluorine atoms and (3) has two to five carbon atoms rather than a single carbon atom.

Angewandte Chemie, vol. 52, page 457 (1939) states that aminobenzotrifluoride and its derivatives when diazotized and coupled with Naphthol AS Grounding components give valuable color tones of exceptional light fastness. The combina tion of one of these aminobenzotrifiuoride bases with Naphthol AS is said to be the red dye used in the German flag. 7

The Angewandte Chemie article refers to German Patents 551,882 (U. S. 1,999,610), 588,781 (U. S. 2,015,204) and 590,255 to illustrated the dye compounds mentioned in the article. These German patents disclose cotton ingrain azo dyes prepared by coupling diazotized aminobenzotrifiuoride compounds with 2,3-oxynaphthoic acid andides (Naphthol AS Grounding components). Although efforts have been made to apply Naphthol AS type dyes to cellulose acetate textile materials, these dye compounds have no utility for cellulose acetate textile materials. The dye compound Compound 2 of tabulation of German Patent 551,882

is typical of the compounds disclosed by the three German patents above mentioned. Henne, in Gilman-Organic Chemistry-42nd ed.page 963 (1943) alludes to the light-fast trifiuoromethyl ingrain azo dyes discussed the Angewandte Chemie article and states that the red dye used in the German flag bears a CFz group on a naphthyl radical.

That many azo compounds having a CFs group are poor dyes for cellulose acetate textile materials will be further apparent from the fact that the following azo compounds yield dyeings on eel- ESQ-2073) M lulose acetate textile materials which have poor iastness to light:

OFa I CHzCHgOH CH CHiOH CHzCHzOH on OH H 02 F8 2 20 GH CHzOH CH OH OH 2 2 a CHzCHzOH CHaClLON SOaCHs CHZCH OH CHgCHZON V CHgCHzOH CHzCHzOH c zCHzOH CHQCHgOH It will be understood that the foregoing dye compounds are merely illustrative of azo compounds containing a CFk group which yield dyeings on cellulose acetate textile materials having poor light fastness. more such compounds.

After much investigation I have discovered that the azo compounds having the formula:

1 BL X Z H SO2NCH:

group 01' a group and Z represents a hydrogen atom, a bromine atom, a chlorine atom, a methyl group oran ethyl group, are valuable dyes for coloring textile materials made of or containing a cellulose aIkyl carboxylic acid ester having 2 to 4 carbon atoms in the acid groups thereof. They are particularly of use for-the coloration of cellulose acetate textile materials. Depending upon their structure, they color the aforesaid textile materials'orange, brownish-orange, scarlet, pinkish-red, red and rubine shades. They dyeings obtained in addition to having excellent fastness to gas possess unusually good fastness to light.

It is an object of my invention to provide new azo dye compounds. Another object is to provide a satisfactory process for the preparation of the new azo. dye compounds of the invention. A further object is to provide dyed cellulose alkyl carboxylic acid ester textile materials which possess very good fastness to light and gas. A particular object to provide new azo compounds which are especially of value for the NOrONHnl and coupling the diazonium compound obtained with a, compound having the formula:

There are many I III R, R1, X, Y and Z in the foregoing formulas have the meaning previously assigned to them.

The aromatic amine compounds having the Formula II that are used in the preparation of the azo compounds of my invention are: pnitroaniline, 4-nitro-2-chloroaniline, 4-nitro-2 bromoaniline, 4-nitro-2-fluoroaniline, 5-nitro-2- aminophenylmethylsulfone, 4-nitro-2-trifiuoromethylaniline, Z-N-methylsulfoneamide 4-nitroaniline, 2-N-ethylsulfoneamide 4 nitroaniline, 4-nitro-2,6-dich1oroaniline, 4-nitro-2-chloro-6- bromoaniline, 4 nitro 2 chloro 6 fluoroaniline, 4 nitro 2 methylsulfone 6 chloroaniline, 4 nitro 2 trifiuoromethyl 6 chloroaniline, 4-nitro-2,6-dibromoaniline, 4-nitro-2- bromo-fi-fluoroaniline, 4-nitro-2-methylsulfonefi-bromoaniline and 4-nitro-2-trifiuoromethylfi-bromoaniline.

Typical of the coupling compounds (Formula III) that are used in the preparation of the azo compounds of my invention are: N-2,2-difluoroethyl N B hydroxyethylaniline, N 2,2- difluoro-n-propyl-N-/3-hydroxyethylaniline, N-3,- 3 difiuoro n propyl N 5 hydroxyethylaniline, N -3,3-difluoro-n-butyl-N- 8-hydroxethylaniline, N-2,2-difluoroethyl-N-pyy-dihydroxypropylaniline, N-2,2-difiuoro-n-propyl-N-;3, -dihydroxypropylaniline, N-3,3-difiuoro-n-propy1-N- 3, -dihydroxypropylaniline,N-3,3-difluoro-n-pr0- propyl-N-fi,' -dihydroxypropylaniline, N-2,2-difluoroethyl N 3 hydroxyethyl m chloroaniline N-2,2 -difiuoro-n-pr0pyl-N-fl-hydroxyethyl-m-chloroaniline, N-3,3-difluoro-n-propyl- N B hydroxyethyl m chloroaniline, N 3,3- difluorobutyl N 13 hydroxyethyl 1n chloroaniline, N -.2,2-difiuoroethyl-N-fiq-dihydroxypropyl-m-chloroaniline, N-2,2-difiuoro-n-propyl-N- pne dihydroxypropyl m chloraniline, N 3,3- difluoro n-propyl N 8, dihydroxypropylm-chloroaniline, N-3,3-difiuo ro-n-butyl-N-B,'ydihydroxypropyl-m-chloroaniline, N.-2,2-difluoro ethyl N ,8 hydroxyethyl m toluidine, N- 2,2 difiuoro n propyl N ,3 hydroxyethylm toluidine, N 3,3 difluoro-n-propyl-N-phydroxyethyl-m-toluidine, N 3,3-difluoro-n-butyl-N-fi-hydroxyethyl-m-toluidine, N-2,2-,difluoroethyl-N,B,v-dihydropropyl-m-toluidine, N-2,2- difiuoro n propyl N W dihydroxypropylm-toluidine, N-3,3-difiuoro-n-propyl-N-fl,-y-dihydroxypropyl m toluidine, N 3,3 difiuoron butyl N 1 W dihydroxypropyl m toluidine, N-4,4-.difluoro-n-amyl-N-p-hydroxyethylaniline, N 4,4 -difluoro n amyl N ,8 hydroxyethyl m chloroaniline, N 2,2 difiuoroethyl N ,3 hydroxyethyl m bromoaniline, N 2,2 difiuoroethyl. N 13 hydroxyethylm-ethylaniline, N-2,2-difluoroethyl-N-v-hydroxypropyl-m-bromoaniline, N -2,2-diflu0ro-n-propy1- N 13 hydroxyethyl In bromoaniline, N 2,2- difiuoro n propyl N p hydroxyethyl methylaniline, N 3,3 difiuoro-n propyl N- fi-hydroxyethyl-m-bromoaniline, N-3,3-difiuoron propyl N p hydroxyethyl m ethylaniline, N 3,3 difiuoro n butyl N 5 hydroxyethyl-m-bromoaniline,N-3,3-difluoro-n-bu tyl-N-;8-hydroxyethyl-methylaniline, N-2,2-difiuoroethyl-N-ay-dihydroxypropyl-m-bromoani line and N 2,2 difluoroethyl N 5,7 .dihydroxypropyl-m-ethylaniline.

It should be here noted that not all azo compounds having a 2,2-difiuoroethylamino group, a 2,2 difiuoro n propylaniino group, a 3,3- difluoro n propylamino group, a 3,3 difluoro-n-butylamino group or a lA-difiuoron-arnylamino group yield dyeings on cellulose acetate textile materials which have good lastness to light. A number of such compounds are referred to hereinafter.

To illustrate, the azo compounds obtained by coupling the coupling compounds of my invention with the diazonium form of 2, l-dinitro- G-chloroaniline, 2,4-dinitro-fi-bromoaniline, 3,5- dinitro-2-aminophenylmethylsulione, 2,4 dinitro-6-trifluoromethylaniline and 6-N-ethylsul=- foneamide-l l-dinitroani1ine yield. dyeings on cellulose acetate textile materials which do not have good fastness to light. Similarly, the azo compounds prepared by diazotizing a compound having the Formula II and coupling the diazonium compound obtained with a compound having the formula:

where R1 represents a 2,2-difluoroethyl group, a 2,2-difiuoro-n-propyl group, a 3,3-difluoro-npropyl group, a 3,3-difluoro-n-butyl group or a 4,4-difluoro-n-amyl group and Q represents a hydrogen atom or a methcxy group yield dyeings on cellulose acetate textile materials which do not have good fastness to light.

Also, the azo compounds obtained by diazotizing o-nitroaniline, Z-nitro-l-chloroaniline and l-nitro-22-hydroxyaniline and coupling the diazoniurn compounds obtained with the coupling compounds of the present invention yield dyeings on cellulose acetate textile materials which do not have good fastness to light.

While the azo compounds of my invention yield dyeings on cellulose acetate textile materials which possess unusually good fastness to light and excellent fastness to gas, those compounds wherein R1 is a 2,2-difluoroethyl group are preferred. In general, these latter compounds, are more light fast than the corresponding compounds wherein R1 is one of the other difluoroallryl groups. Again, those compounds wherein E. is a e-hydroxyethyl group are preferred because they are, in general, more light fast than the corresponding compounds wherein R is a -hydroxypropyl group or a pndihydroxypropyl group- From the foregoing, it logically follows that those compounds wherein R and R1 are simultaneously a 2,2-difluoroethyl group and a c-hydroxyethyl group, respectively, are preferred. i

The following examples illustrate the ace compounds of my invention and their manner of preparation.

EXAMPLE I A. Preparation of nitrosyl sulfuric acid 7.6 grams of dry sodium nitrite were added with stirring to 50 cc. of sulfuric acid (sp, gr. 1.84:) while keeping the temperature below 70 C. The resulting reaction mixture was then cooled to 15 C.-20 C. and 100 grams of acetic acid were added dropwise with'stirring, follow- 6 ing which the reaction mixture was cooled to 3 0-10" 0. B. Diazotz'zation 21.6 grams of finely powdered 5-nitro-2- aminophenyl-methylsulfone were added slowly, with stirring, to the nitrosyl-sulfuric acid reaction mixture prepared as described above. :Ihe reaction temperature was maintained below 20 C. After the addition of the amine, 00 grams of acetic acid were added dropwise with stirring and the reaction mixture was stirred at 15 C.- 20" C. until all of the amine had dissolved and the diazotization reaction which takes place was complete. The diazonium solution was then poured onto 500 grams of crushed ice, and enough urea or sulfamic acid was added to destroy the excess nitrous acid. The diazonium solution should be clear and free of suspended undiazotized amine.

C. Coupling v 10 grams of sulfuric acid (sp. gr. 1.84) were added to 20 cc. of water and the resultin solution was cooled to 5 C. and then 20.1 grams of N-2,2-difluoroethy1-N c hydroxyethylaniline were added while cooling. When solution was complete, 200 grams of crushed ice and 200 cc. of ice cold water were added to the reaction mixture. Then the diazonium solution prepared, as described above, was added with stirring. Upon completion of the coupling reaction which takes place, sufficient sodium carbonate to neutralize the mineral acid present was slowly added to the reaction mixture. Suficient diazonium solution should be used to give a slight positive test (for a, diazo solution) when all the coupling component has reacted. The dye compound formed was recovered by filtration on a Biichner funnel, washed free of salts with water and air dried. The yield of dye melting at C.-l30 C. was 40.6 grams. It has the formula:

CHzCHF GH CHZOH CHzCHFz CHICHFZ 302C113 colors cellulose acetate textile materials yellowish-orange shades which have poor fastness to light. 1

EXAMPLE 2 A. Dz'aeotizatz'on 17.3 grams or" l-nitro-Z-chloroaniline' were stirred into a solution of 7 cc. of sulfuric acid 7 Isa-gr. 1.84) in 200 cc. .of water. Suflicient ice was added to maintain a temperature of C.10 C. during the diazotization which was performed .byadding a solution of 7.5 grams of sodium nitritedn cc. of water. Stirring was continued during the ,diazotization .reaction and when the diazotization reaction was. complete, the reaction mixture was filteredand any excess nitrous acid was. destroyed by adding urea or sulfamic acid.

B. Coupling lokgrams of sulfuric'acid (sp. gr. 1.84) were added to 20 cc. of water and the resulting solution was cooled to 5C. and then 20.1 grams of N-2,2 -difluoroethyl-N-fi-hydroxyethylaniline were added'while cooling. When solution was complete, IOOgrams of crushed ice and 100 grams of ice cold water were added to the reaction mixture. Then the diazonium solution prepared as described above was added with stirring. Upon completion of the coupling reaction which takes place, sufiicient sodium carbonate to just neutralize the mineral acid present was added. Sufficient diazonium solution should be used to give as'light positive test (for a diazo solution) when all. the coupling component has reacted. The dyecompound formed was recovered by filtration on a .Biichnerfunnel, washed free of salts with water and dried. The yield of dye melting at 150 C.-154 C. was 37.4 grams. It has the formula:

V p OHZOHF, NOr-QN=N-ON CH:CHzOH and colors cellulose acetate textile materials scarlet shades.

By the use of 21.7 grams of 4nitro-2-brom0 aniline and 15.6 grams of 4-nitro-2-fluoroaniline, respectively, in place-of 4-.nitro-2-chloroaniline azo dye compounds are obtained which color cellulose acetate textile materials scarlet shades.

EXAMPLE 3 A. Diazotizatiom.

B. Coupling 20.1 grams of N-2,2-difluoroethyl-N-B-hydroxyethylaniline were dissolved in 300 cc. of 12 sulfuric acid. The resulting solution was cooled to 0 C.10 C. by adding crushed ice with stirring. Then the diazonium solution prepared as described above was added to the reaction mixture with stirring. Coupling takes place rapidly. The reaction mixture was cooled, with crushed ice, for example, as needed, to keep the reaction temperature at about 10 C.-15 C. The reaction mixture was stirred for about one-half hour after the addition of thediazonium solution and then slowly made neutral to Congo red paper with sodium bicarbonate after which it was allowed to stand for 1 hour. The dye compound formed was a recovered .byfiltration, washed .free of any salts with water and dried. The azo dye compound thus obtained has the formula:

It colors cellulose acetate textile materials orange shades which have excellent fastness to light and gas.

By the use of 21.5 grams of N-2,2-difluoro'-npropyl-N-;9-hydroxyethylaniline in place of N- 2,2 difluoroethyl-N p-hydroxy-ethylaniline, an azo dye compound is obtained which colors cellulose acetate textile materials orange shades which have excellent fastness to light and gas.

By way of contrast, the azo compound of the formula:

01 I I /CH2CH:OH

| OH CF OH NO, a z 2 colors cellulose acetate textile materials orange shades which have poor fastness to light.

EXAMPLE 4 24.1 grams of 4-nitro-2-trifiuoromethyl6-chloroaniline are diazotized inaccordance with the procedure described in Example 3 and the diazonium compound obtained is coupled with 20.1 grams of N-2,2-difiuoroethylN- 3-hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance'with the procedure describedin Example 3. The dye compound obtainedcolors cellulose acetate textile materials brownish-orange shades.

By the use of 21.5 grams of N-2,2-difluoroethyl-N--, -hydroxypropylaniline and 24.5 grams of N-2,2-difiuoroethyl-N-fl,'y-dihydroxypropylaniline, respectively, in place of N-2,2-difluoroethyl- N -,B-hydroxyethylaniline,' dye compounds are obtained which similarly color cellulose acetate textile materials brownish-orange shades.

EXAMPLE 5 28.5 grams of 4-nitro-2-trifluoromethyl-6 bromoaniline are diazotized in accordance with the procedure described in Example 3 and the diazonium compound obtained is coupled with 21.5 grams of N2,2-difluoroethyl-N-B-hydroxyethylm-toluidine. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 3. The dye compound obtained colors cellulose acetate textile materials brownish-orange shades.

By the use of 20.1 grams of N-2,2-difluoroethyl-N -p-hydroxyethylaniline and. 21.5 grams of I I3-,'3-d1fluoro-npropyl-N p hydroxyethylaniline, respectively, in place of N-2,2-difluoroethyl- N-fi-hydroxyethyl-m-toluidine, dye compounds are obtained which color cellulose acetate textile materials brownish-orange shades.

EXAMPLE 6 21.6 grams of 5nitro-2-amino hen sulfone are diazotized in accord hcew i t i t e procedure described inv Example 1 and the diazomum compound obtained is coupled with 25 9 grams of N 3,3 difiuoro n butyl-Nfl Y-dihy 9 droxypropylanilme. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Examline, respectively, in place of N-3,3-difluoro-nbutyl-N-,8,y-dihydroxypropylaniline, dye compounds are obtained which color cellulose acetate textile materials rubine shades.

EXAMPLE 7 17.3 grams of 4-nitro-2-chloroaniline are diazotized in accordance with the procedure described in Example 2 and the diazonium compound obtained is coupled with 24.3 grams of N-A-difluoro-n-amyl-N-18-hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 2. The dye compound obtained colors cellulose acetate textile materials rubine shades which have excellent fastness to light and gas.

By the use of 13.8 grams of p-nitroaniline in place of 4-nitro-2-chloroaniline, a dye compound is obtained which colors cellulose acetate textile materials orange shades which have very good fastness to light and gas.

By contrast, the azo compound of the formula:

CH CHaCHgC FzCHa CHgCHsOH colors cellulose acetate textile materials rubine shades which have poor fastness to light.

EXAMPLE 8 ethyl-Np-hydroxyethylaniline, dye compounds.

are obtained which color cellulose acetate textile materials red shades.

EXAMPLE 9 26.5 grams of 4-nitro-2-trifluoromethylaniline are diazotized in accordance with the procedure described in Example 2 and the diazonium compound obtained is coupled with 24.9 grams of N-3,3-difiuoro-n-propyl -'N fl-hydroxyethyl-mchloroaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 2. The dye compound obtained colors cellulose acetate textile materials red shades.

By the use of 29.4 grams of N-3,3-difiuoro-npropyl-N p hydroxyethyl m bromoaniline in place of l T-3,3-difluoro-n-propyl-l T- &-ltlydroxyethyl-m-chloroaniline, a dye compound is obtained which colors cellulose acetate textile materials red shades.

EXAMPLE 10 20.6 grams of 4nitro-2etrifiuoromethylaniline are diazotized in accordance with the procedure described in Example 2 and the diazonium compound obtained is coupled with 27.3 grams of N-2,2-difiuoroethyl-N- 3,y dihydroxypropyl-methylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 2. The

dye compound obtained colors cellulose acetate textile materials rubine shades. 7

By the use of 25.9 grams of N-2,2-difiuoroethyl- N-Bry-dihydroxypropyl-m-toluidine in place of N-2,2-difiuoroethyl-N-,B,y dihydroxypropyl-methylaniline, a dye compound is obtained which colors cellulose acetate textile materials rubine shades.

EXAMPLE 1 1 21.6 grams of 5-nitro-2-aminophenylmethylsulfone are diazotized in accordance with the procedure described in Example 1 and the diazonium compound obtained is coupled with 25.9 grams of N -2,2-difiuoroethyl N-fi/Y dihydroxypropyl-mtoluidine. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. compound obtained colors cellulose acetate textile materials rubine shades.

By the use of 27.3 grams of N-2,2-difiuoroethyl- "3 7- ydroxyl ropyl-m-ethylaniline inplace of N -2,2-difluoroethyl N-flrv dihydroxypropyl-mtoluidine, a dye compound is obtained which colors cellulose acetate textile materials rubineshades.

EXAMPLE 12 CHzC FgCH:

OHZCHZOH N02 colors cellulose acetate textile materials rubine shades which have poor fastness to light.

EXAMPLE 13 20.7 grams of l-nitro-2,6-dichl0roanilin are diazotized in accordance with the procedure described in Example 3 and the diazonium compound obtained is coupled with 24.9 grams of N 2,2 difiuoro n propyl N [3 hydroxyethyl-m-chloraniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Exam- The dye of l-nitro-2-trifluoromethyl-6-' ple'B. "I'hccdye compound obtainedcolors cel- "20.1 grams of 4-nitro-2,6-dichloroaniline are diazotizedinaccordance with the procedure described in Example 3 and the diazonium compound obtained is: coupled with 26.3 grams of N 333 difluoro n butyl N {3 hydroxyethyl-m-chloroaniline. Coupling and recovery of: the dye compound formed is carried out in accordance with the procedure described in Examp16 3. The dye compound obtained colors cellu- .lose acetate textile materials orange shades.

EX-AIVBPLE 15 grams of 4-nitro-2-fluoro-6 chloroaniline aredia zotized in accordance with the procedure described in Example 3and the diazonium compound obtained is coupled with 20.1 grams of N 2,2 difiuoroethyl N fi hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the-procedure described in Example 3. The dye compound obtained colors cellulose acetate textile materials orange shades.

By' the use of 25.7 grams of N-4A-difluoro-namyl-N-'y-hydroxypropylaniline in place of N- 2,2 difiuoroethyl N B hydroxyethylaniline, a. dye compound is obtained which colors cellulose acetate textile materials orange shades.

13.8 grams of p nitroaniline are diazotized in accordance with the procedure described in Example -2andthediazonium compound obtained EXAMPLE 17 25.1 grams of 4-nitro=2-methylsulfone-6-chloroaniline are diazotized in accordance with the procedure described inExample 3 and the diazonium compound obtained is coupled with 20.1 grams of N 2,2 difluoroethyl N 3 hydroxyethylaniline. -.Coupling and recovery of the dye compound formedis carried out in accordance with the procedure described in Example 3. The dyecompound obtained colors cellulose. acetate textile materials orange shades.

12 By the use of 21.5 grams of N2,2.-.difluDrO-rn-1 propyl-N-c-hydroxyethylaniline in place of N-.-. 2,2-difluoroethyl-N-p-hydroxyethylaniline a dye compound is obtained which colors cellulose ace.-

tate textile materials orange shades.

EXAMPLE 18 29.6 grams of 4-nitro-2-methylsulfonee6- bromoaniline are diazotized in accordance with the procedure described in Example 3 and the diazonium compound obtained is coupled with 25.9 grams of N-3,3-difiuoro-n-propyl-N-B,'ydihydroxypropylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 3.v The dye compounds obtained colors cellulose acetate textile materials orange shades.

By the use of 21.5 grams of N -2,2-difiuoroethyl- Nrfi-hydroxyethyl-m-toluidine in place of N-3,3 difluoro n propyl N Brr dihydroxypropyle aniline, a dye compound is obtained which colors cellulose acetate textile materials, orangeshades.

EXAIVLPLE 19 24.5 grams of 2N-ethylsulfonamide-4-nitroaniline are diazotized in accordance with they procedure described in Example 1 and the diazonium compound obtained is coupled with 20.1 grams of N-2,2-difiuoroethyl-N-[i-hydroxyethyl aniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials red shades which have very good fastness to light.

By the use of 27.3 grams of N-3,3-difluoro-nbutyl-N-pw-dihydroxypropylaniline in place of N -2,2-difluoroethyl-N -5-hydroxyethylaniline, a dye compound is obtained which colors cellulose acetate textile materials red shades which have very good fastness to light.

By contrast, the azo compound of the formula:

/CH2CH2CF2CH3 H 1 H CH CHOHCH OH sol\ ogn5 2 2 colors cellulose acetate textile materials reddishviolet shades which have poor fastness to light.

EXAMPLE 20 23.1 grams of 2-N-methylsulfonamide-4-nitroaniline are diazotized in accordance with the procedure described in Example 1 and the di-v azonium compound obtain-ed is coupled with 20.1 grams of N-2,2-difiuoroethyl-N-c-hydroxyethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate textile materials red shades.

By the use of 22.9 grams of N-3,3-difluoron-butylN-s-hydroxyethylaniline in place of N- 2',2-di1iuoroethyl-N-fi-hydroxyethylaniline, a dye compound is obtained which colors cellulose acetate textile materials red shades.

Following the procedure described in Examples 1 to 20, inclusive, the dye compounds indicated hereinafter were prepared. The color is that which the dyes give on cellulose acetate textile materials.

Diazo Component Coupling Component Color nitro 2 aminophenyl metli- N 3,3 difiuoro n butyl Rubine.

ylsulfone. N B hydroxyethyl in toluidine. Do N 2,2 difluoroethyl N B Do.

hydroxyethyl m tolui- (line. 4 nitro 2 trifluoromethylaui- N 2,2 difiuoroethyl 7 Red.

line. 'y hydroxypropylanilme.

Do N 3,3 diiluoro n butyl Do.

N B hydroxyethylani line. Do N 3,3 difluoro n butyl Do.

N 5, dihydroxypropylaniline. Do N 2,2 diiluoroethyl N -,8 Do.

hydroxyethyl In chloroaniline. Do N 2,2 difiuoroctliyl N B Rubine hydroxyethyl In toluidine. Do N 2,2 difluoroethyl N 13, Do.

7 dihydrcxypropyl In toluidin c. 4 nitro 2 triiluoromethyl 6 N- 2,2 di uoroethyl N -5 chloroaniline. l ydroxyethyl m tolui- 1116. Do N 2,2 difiuoroethyl N 8 Do.

hydroxyethyl m chloroaniline. 4 nitro 2 trifluoromethyl 6 N 2,2 dlfluoro n propyl Do.

chloroaniline. N B hydroxyethyl m chloroam'line. Do N 2,2-difluoro-n-propyl Do.

1N 'y hydroxypropylaniine. -nitrcaniline N 2,2 difluorocthyl N B Orange.

hydroxyethylaniliue. 4 nitro 2,6 dichloroanilineuu N 3,3 difluorc n butyl Do.

in) ,6 hydroxyethylanime. Do N 4,4 difluoro n amyl Do.

1N B hydroxyethylanime. 5 nitro 2 aminophenyl- N 4,4 difiuoro n amyl; Rubine.

methylsulione .l B hydroxyethylamme. Do.-., N- i,4-difiuor0 -n-amyl- Do.

N B hydroxyethyl In toluidine.

While not all of the compounds of my invention have been specifically described, the manner of preparing any of the compounds is believed to be obvious from the numerous examples given hereinbefore.

Dye compounds corresponding to those described hereinbefore but which contain at least one -OSO3H group or this group in its salt form have also been prepared. These dye compounds containing a sulfato group are prepared either by introducing a sulfato group into the dye compounds previously described or by introducing a sulfato group into the coupling components of the present invention and coupling the compounds thus obtained with the diazonium compounds used in the preparation of the new azo compounds of the invention. These new dye compounds are suitable for dyeing the textile materials mentioned hereinbefore as well as silk, wool and nylon textile materials. Because of the increased water solubility of these new dye compounds, they are particularly adapted for dyeing cones of yarn and fabrics of close weave and of heavy construction.

The following examples illustrate the manner in which these new sulfato dye compounds are prepared.

EXAMPLE 21 42.7 grams of CHECHFQ g CHZCHQOH OzCHz are dissolved in 500 cc. of carbon tetrachloride and the resulting solution is cooled to C.

Then 12.7 grams of freshly distilled chlorosulionic acid are added dropwise with stirring over a period of 3 hours. After the addition of the chlo rosulfonic acid, the reaction mixture is slowly warmed to 50 C. and maintained at this temperature for several hours. Heating is then discontinued and the carbon tetrachloride is distilled off under reduced pressure. 300 cc. of ice and water are then added to the reaction mixture and the dye is recovered by evaporation. If a salt form of the dye is desired, the evaporation step is omitted. Instead, following the addition of the 300 cc. of ice and water, the reaction mixture is neutralized with sodium hydroxide (other suitable organic or inorganic bases can be used) warmed to dissolve the dye, filtered to remove any insoluble material and then concentrated under reduced pressure until the dye separates. The dye compound thus obtained has the formula:

onions,

\CH2CH2OSO3NEL SOgOHs It colors cellulose acetate, wool, nylon and silk textile materials red shades from an aqueous solution or suspension.

chlorosulfonic acid are added dropwise with stirring over a period of 3 hours. Stirring is continued for an additional 2 hours following which the reaction mixture is heated to 50 C. and main-- tained at this temperature for two'hours.- Fol lowing this the reaction mixture is cooled and the pyridine is removed under reduced pressure. 300 cc. of ice and water are then added to the reaction mixture and the dye is recovered by evaporation. The dye compound obtained colors cellulose acetate textile materials scarlet shades.

EXAMPLE 23 EXAMPLE 24 20.6 grams of 4-nitro-2-trifluoromethylaniline are diazotized in accordance with the procedure described in Example 2 and the diazonium compound obtained is coupled with 42.7 grams of the sodium salt of N-2,2-difluoro-n-propyl-N-fi-sulfatoethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 2. The dye compound obtained colors cellulose acetate, wool, silk, and nylon red shades.

EXAMPLE 25 45.7 grams of the dye compound obtained as described in Example 19 are dissolved in 500 cc. of carbon tetrachloride and the resulting solution is cooled to 10 C. Then 12.7 grams of freshly distilled chlorosulfonic acid are added dropwise with stirring over a period of 3 hours. After the addition of the chlorosulfonic acid, the reaction mixture is slowly warmed to 50 C. and maintained'at this temperature for several hours. Heating is then discontinued and the carbon tetrachloride is distilled oil" under reduced pressure; 300cc. of ice and water are then added to the reaction mixture after which the reaction mixture is neutralized with an aqueous sodium hydroxide solution, warmed to dissolve the dye, filtered to remove any insoluble material and then concentrated under reduced pressure until the dye separates. The dye compound thus obtained has the formula:

CHQCEFE Noe Meg It colors cellulose acetate, wool, nylon and silk textile materials red shades.

EXAMPLE 26 44.3 grams of 2-(N-methylsulfonamide)-4- nitrobenzeneazo N 2,2 difluoroethyl-N-fi-hydroxyethylaniline (dye of Example 20) are dissolved in 200 cc. of pyridine and the resulting solution is cooled'to 5 C. Then 12.7 grams of chlorosulfonic acid are added dropwise with stirring over a period of 3 hours. Stirring is continued for an additional 2 hours following which the reaction mixture is heated to 50 C. and maintained at this temperature for two hours. Following this the reaction mixture is cooled and the pyridine is removed under reduced pressure. 300 cc. of ice and water are then added to the reaction mixture and the sulfate dye compound 16 is recovered by evaporation. It colors cellulose acetate, wool, nylon and silk textile materials red shades.

By the use of 51.5 grams of Z-(N-ethylsulfonamide) 4 nitrobenzeneazo-N3,3-difluoro-nbutyl-N-fi,'ydihydroxypropylaniline in place of Z-(N-methylsulfonamide) 4 nitrobenzeneazo- N 2,2-difiuoroethyl-N -fihydroxyethylaniline in the above example, a dye compound is obtained which colors cellulose acetate, wool, nylon and silk textile materials red shades.

EXAMPLE 27 23.1 grams of 2N-methylsulfonamide-4-nitroaniline are diazotized in accordance with the procedure described in Example 1 and the diazonium compound obtained is coupled with 33.1 grams of the sodium salt of N-3,3-difluoro-nbutyl-N-,8-sulfatoethylaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate, wool, nylon and sill; red shades.

EXAMPLE 28 24.5 grams of 2-N-ethylsulfonamide-4-nitroaniline are diazotized in accordance with the procedure described in Example 1, and the diazonium compound obtained is coupled with 33.7 grams of sodium salt of N-2,2-difluoroethyl-N- fi-sulfatoethyl m chloroaniline. Coupling and recovery of the dye compound formed is carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate, Wool, nylon and silk red shades.

By the use of 34.5 grams of the sodium salt of N-4,4-difluoro-n-amyl-N-B-sulfatoethylaniline in place of the sodium salt of N-2,2-difluoroethyl- N-B-sulfato-mchloroaniline. In the above example a dye compound is obtained which colors cellulose acetate, wool, nylon and silk red' shades.

EXAMPLE 29 the dye compound formed is carried out in ac-' cordance with the procedure described in Example l. The dye compound obtained colors cellulose acetate, wool, nylon and silk rubine shades.

By the use or" 31.7 grams of the sodium salt of N-2,2 -difluoroethyl-N- -sulfatopropylaniline in place of the sodium salt of N-2,2-difluoroethyl N B sulfatoethyl m toluidine. In the above example a dye compound is obtained which colors cellulose acetate, wool, nylon and silk red shades.

From the foregoing examples the manner of introducing e, sulfate group into any of the azo compounds of my invention is believed to be clear, especially since the manner of introducing a sulfato group is known to those skilled in the art. Any other suitable way of introducing the sulfato group into the dye molecule can be employed. The sulfato group can be present in its free acid form or in the form of an inorganic or organic base salt such as, for example, the Na,

NILi, Mg, Ca, Li, methylamine, dimethylamine, trimethylamine, pyridine, aniline, guanidine, semicarbazide, biguanidine, phenyl guanidine, cyclohexylamine, dioyclohexylamine, tetrahydrofuriurylamine or alkanolamine salt form,

In order that the preparation of the azo compounds of my invention may be clearly understood, the preparation of certain intermediates used in their manufacture is described hereinafter. i

EXAMPLE A 4-m'tro-2-trifluoromethyl-d-chloroaniline 990 grams of concentrated hydrochloric acid and 500 grams of glacial acetic acid were placed in a 2-liter flask equipped with a chlorine inlet tube, a gas escape tube attached to a water trap, a mechanical stirrer, a thermometer and a cooling bath. Then 206 grams of finely powdered 4- nitro-2-trifluoromethylaniline were added to the mixed acids. The reaction mixture was cooled to C. and about 73 grams of chlorine were gradually introduced with vigorous stirring over a period of 4 to 6 hours while keeping the temperature between 10 C.- C. The reaction proceeded rapidly without much evolution of heat and 4-nitro-2-trifiuoromethyl-6-chloroaniline separated as a fine yellow solid. Toward the end of the chlorination, the rate of addition of chlorine was materially lowered to avoid decomposition of the 4-nitro-2-trifluoromethyl-6- chloroaniline.

When about 73 grams of chlorine (or until a sample gives the desired melting point) had been absorbed, the chlorine addition was stopped and the reaction mixture stirred for one hour to complete the reaction. The reaction mixture was then filtered on a Biichner funnel to recover the precipitated '4-nitro-2-trifiuoromethyl-6-chloroaniline. The filter cake was washed with 100 grams of acetic acid and then with'l75 grams of water.

After drying, the compound melted at 112 C.- 114 C. and after crystallization from acetic acid it melted at 115 C.-116 C. The yield of 4- nitro-Z-trifiuoromethylfi-chloroaniline was 228 gramswhich is 95% of the theoretical.

EXAMPLE B A 4-1iz'tro-2t1'ifluoromethyl-6-bromoaniline 20.6 grams of 4-nitro-2-trifiuoromethylaniline were dissolved in 100 cc. of acetic acid and 16.8 grams of bromine in 100 cc. of acetic acid were gradually added at 40 C. The reaction mixture was placed: on a steam bath for 4 hours under acondenser. Then it was cooled and poured into ice water. 4-nitro-2-trifiuoromethyl-fi-bromoaniline precipitated as a yellow solid and was recovered by filtration. The filter cake was washed with a water solution of NaHsOz,

then with water and dried. It melted at 140 C.-142 C. The yield was 26 grams.

EXAMPLE C -m't'ro-Z -methylsulfone-6-chloroaniline temperature at about C. C. Chlorine was bubbled in for about 4% to 5 hours and then the reaction mixture was drowned in cold water.

4-nitro-2-methylsulfone-6-chloroaniline precipitated and was recovered by filtration. It was washed with cold water, then with a saturated solution of NaHSOa and finally with water. Upon drying and recrystallization from glacial 18 acetic acid the product melted at 224 C.-225.5 C. Before recrystallization it melted at 214 C. 216 C. The yield was 4.7 grams.

EXAMPLE D -nitro-2-methylsulfone-6-b1'omoaniline 21.6 grams of 5-nitro-2-aminophenylmethylsulfone were placed in 200 cc. of glacial acetic acid and 16.5 grams of bromine were added dropwise with stirring. After about 6 hours the reaction mixture was warmed on a steam bath under a condenser. After 30 minutes the reaction mixture was cooled, poured into water and filtered. 4-nitro-2-methy1sulfone 6 bromoaniline was obtained as yellowish crystals which were washed with aqueous NazCO3 and dried. If desired, a purer product can be obtained by crystallization from hot acetic acid.

EXAMPLE E 4-m'tro-2-chloro-6-fluoroaniline grams of concentrated hydrochloric acid (sp. gr. 1.14), 50 grams of glacial acetic acid and 15.6 grams of 4-nitro-2-fiuoroaniline were placed in a 3-necked 500 cc. round-bottomed flask, fitted with a stirrer and a thermometer. The reaction mixture resulting was cooled to 10 C.15 C. and chlorine was slowly introduced to the stirred reaction mixture at 10 C.- 15 C. until 7.5 grams had been taken up. This usually takes 2-4 hours. Stirring was continued for an additional hour and then the insoluble reaction product was recovered by filtration, washed with acetic acid and water and dried. 18.5 grams of 4-nitro-2-ch1oro-6-fluoroaniline were recovered as a yellow crystalline solid. It melts at C.-127 C.

If desired, the chlorination can be carried out in a dilute sulfuric acid medium.

EXAIVIPLE F 4-nitro-2-brom0-defluoroaniline This compound is obtained by the use of bromine in place of chlorine in Example E. It is a yellow crystalline solid.

Compounds having the formula:

OHZCHZOH are prepared by reacting ethylene oxide witha compound having the formula:

R1 and Z in the foregoing formulas have the means previously assigned to them.

The following examples are illustrative of the manner in which the compounds of the formula numbered IV are prepared.

fiuoro'ethyl-N-B-hydroxyethylaniline. z.- boi1ing.. at;

123.1C.-125:C./3 mm.; were. obtainedzs. About: 1.5 .1 grams of N-2,2--difluoroethylaniline were. 3.150.167';

covered. 7

EXAMPLE -H N -2,2-difluoro-n-propyl-N fi-hydrozcyethyk aniline 7.9 grams of N=2,2 difiuoro-n-propylaniline,- 1.9 grams of ethylene oxide and 10 cc. of ethyl;

alcohol'were heated with shaking in a sealed tube for 8 hours at 185C. The contents of the tube were cooled, 'removed from thetube and distilled under reduced pressure. About 3 gramsaniline boiling at, '155--'C; -160 C./11 mm. were obtained.

EXAMPLE I N-2,2-difluoro-n-propyl-N-p-hydroxyethylm-chloroaniline' 7.6 grams of N-2,2--difiuoron-propyl-m-chloroaniline, 1.9 grams of. ethylene oxideand. 5 cc.

ofethylalcoholowere heated with shakingin a sealed tube for 15 hours at 200 C.. Thenthe.

contents of, the tube..\vere cooled,.removed from...

the ,tube and distilled .under reduced pressure.

droxyethylem-ch1oroanil-ine. boiling at 165. C.

170 C.-/6 mmrwere obtained.

. EXAMPLE .J

and-1L4 grams of. ethylene oxide" dissolved in .10

cc. of ethyl alcoholwere. heated. in a sealed tube at.180.,C. for 24 hours. Theresulting reaction mixture was fractionated under. reduced pressure in a small helix-packed column. difiuoro-n-butyl-N-,8-hydroxyethylaniline, boiling point 140 C.-l4 3 C./1.5 mm., n 1.5142, was obtained in 84% yield.

EXAMPLE K 10 grams of N-4,4-difluoro-n-amylaniline, 2.6 grams of ethylene oxide and 10 cc. of ethyl alcohol were heated, withshaking ina sealed tube at 200 C. for 15 hours. The reaction mixture was cooled, removed from thetube and distilled under reduced pressure. 10 gramsofN-ifl-dianiline, B; P. 165 C.-l68. C./1 mm.;- N-3,3-..

difiuoro-n-pro-pyl N e hydroxyethylaniline,

propyleNefl-hyd-ro xyethyl-m:toluidine, :B. .P.

aniline, B. P. 131 'C..-'132E C./1 mm.; etc., are prepared.

Compounds having the formula:

wherein R1 .andxz have the meaning,..previously.

assigned to themcare prepared .by. reacting .-tri.-:1 methylene .chlorohydrin or trimethylene bromo-: hydrin with, a compound-having the. formula: :,.V

The following: examples are illustrative .of the r manner/in .which 3 the compounds havingathe formula; numbered -:VI are; prepared; 1

N-'-3,3 difluoro n propyl N- -hydroxypropylg" aniline 51.3 grams of N-3,3-difluoro-n-propylaniline1..

and :30 grams .or-trimethylene chlorohydrin .were heated :together on a steam .bath..for '10. hours.

The reaction mixture was cooled and.10.%- aque ous NaOHwas added thereto untilit was-,alka-- line. The -reaction mixture was -treated with. benzeneandthe benzeneportion was removed washed with water andthendistilled under re-.- .duced pressure." N -3,3-.difiuoro n propyl-N-v hydroxy-propylaniline -boiling at. 122 C.l26. C./12 mm. was obtained.

EXAMPLE. M.

v,lV 2,2 diflzioroethyl J N '-y hy'drowypropylam 51.3 grams ofN-2,2-difluoroethyl-m-toluidin'e were reacted with 30 grams of -trimethylene chlorohydrin in accordance with the procedure described in Example L. -N-'2,2-difluoroethyl-N-yhydroxypropyl-m-toluidineboiling ,at 134 C.-; 138 C.-/2 mm. wasobtained.

EXAMPLE ..N

N-'2,2-difluoro n propyb- N-w-hydroxypropiyle.

aniline 51.3v grams. of N2.2:difiuoro-n-propylaniline, 46.4 grams of. trimethylenebromohydrin and 30.5 gramsof -.NaHCOa were. heated at C. for .6

hours with. stirring. Upon cooling, benzene was.-. added to the reaction mixture and, the reaction mixture was filtered. The benzene was removed from the filtrate and the;portion remaining was distilled under reduced pressure to obtain N-2,2- difluoro n propyl-N v hydroxypropylaniline boilingiat 137 Ct-140 '-C./1 mm...

Followingtheprocedure described in Examples L, M: and i N, N-2,2-difluoro-n-pr0pyl-N-'y-hy droxypropyl-m-chloroaniline, N 2,2-difiu0ro-n-.-- propyl-N-v-hydroxypropyl m toluidine, N-3,3-

m toluidine boiling at 183 C.186 C./6 1111111.,v

N-3,3-difiu0ro-n-'but-yl N 'y hydroxypropyl--- m.--chloroaniline-boiling at 190 C.-C./6 mm.; N 2,2 difluoroethyl-N" -hydroxypropylaniline boiling-at 117--C.-.l21 C./1-2 -mm., and. N-3,3= difluoro-n-buty1-N-- -hydroxypropylaniline. boi1-.. .ying at178-C.-180? :C.-/6 mm.-.are.obtained.

- EXAMPLE N-4,4-difluoro-n-amyl-N-v-hydroxypropylaniline 100 grams of N-4,4-difluoro-n-amylaniline and 30 grams of trimethylene chlorohydrin were.

heated together on a steam bath for hours. The reaction mixture was cooled and made just basic by adding 10% aqueous -NaOH. Benzene wasadded to the reaction mixture and the reaction mixture was filtered. The filtrate was washed with water and the benzene portion was distilled under reduced pressure. N-4,4-difiuoroe n -.amyl N 'y hydroxypropylaniline boiling at 180 C.-185 C./7 mm. was obtained. It is a heavy colorless liquid. 7

Similarly N-4,4-difluoro-n-amyl v hydroxypropyl m chloroaniline and N-4,4-difluoro-namyl-'y -hydroxypropyl-m ethylaniline, B. P. 185 C.-189 C./6 mm., for example, are obtained.

Compounds having the formula:

EXAMPLE P aniline 17 grams of N-2,2 difluoro-n-propylaniline, 1 0 grams of NaI-ICOs, 100 cc. of amyl alcohol and 12-grams of glyceryl chlorohydrin were heatedv together under refluxing conditions for 6-10 hours. Then 2 grams of charcoal were added.

and the reaction mixture was stirred and filtered to remove the charcoal, salt and any other in, soluble material. -The amyl alcohol was removedby distillation under reduced pressure and then 1 the reaction mixture was steam-distilled under; reduced pressure to remove any unchanged N- 2, 2-difluoro-n-propylaniline. Following this the reaction mixture was extracted with benzene and the benzene extract was distilled to dryness under reduced pressure. N-2,2-difluoro n propyl-N- p, -dihydroxypropylaniline was obtained. It is a straw colored, viscous compound.

EXAMPLE Q aniline 9 grams of N-3,3-difluoro-n-buty7laniline and 4.6 grams of NaI-ICOs were stirred and heated together at 145 C. by means of an oil bath while 6.1 grams of glyceryl chlorohydrin were slowly added. After the addition, heating and stirring at 145 C. were continued for 6 hours. The evolution of carbon dioxide ceased after an hour. An equal volume of water was then added to the reaction mixture and the reaction mixture was extracted three times with benzene. The benzene solution was steam-distilled, leaving the reaction product as an oily residue. N 3,3-difluoro-n-butyl-N-B,' -dihydroxypr0pylaniline was 95%. Upon distilling the crude product in a molecular still (i. e. a Hickman molecular still manufactured by Distillation Products, Inc.,

Rochester, N. Y.) under a'reduced pressure of 1 The yield of crude I 2 chloroethane, 3,3 difiuoro n-propylbromide 2 22 microns at C.- 0., N-3,3-difluoro-nbutyl-N-fl -dihydroxypropylaniline was obtained as a clear, very viscous oil No 1.5230.

EXAMPLE R 12 grams of N-3,3-difluoro-n-butyl-m-}toluidine, 5.6 grams of NaI-ICO: and 7.3 grams of glyceryl chlorohydrin were heated to ether at C. for 7 hours in accordance, with the pr0-. cedure described in Example P. The crude reactionproduct-thus obtained was distilled in a molecular still (i. e. a Hickman molecular still manufactured by Distillation Products, Inc.-, Rochester, N. Y.)'under a reduced pressure of 11-14 microns at a temperature of 110 C. N- 3,3 difluoro n butyl-N-fi,v-dihydroxypropylm-toluidine was obtained. Upon recrystallization from hexane it melted at 81 C.

EXAMPLE S This compound was obtained by reacting 10.3

grams of N 2,2 difiuoroethyl-m-toluidine. 5.6 grams of NaHCOa and 7.3 grams of glyceryl ch1orohyclrin together in accordance with the procedure described in Example Q. 1

EXAMPLE T N-4,4-difluoro-n-amyl-N-e,y-dihydromypyropylanilz'ne 20 grams of N-4,4-difluoro-n amylaniline, 10 grams of NaHCOa, 100 cc. of amyl alcohol and 12 grams of glyceryl chlorohydrin are heated together under refluxing conditions for 6 -10hour's.

Then 2 grams of charcoal are added and the re action mixture is stirred and filtered to remove the charcoal, salt and any other insoluble material. Upon working up the reaction mixture in accordance with the procedure described in Example P, N 4,4 difluoro-n-amyl-N-fi,'Y-dihy= droxypropylaniline is obtained.

It is a strawcolored, very viscous compound. V

Following the procedure described in Examples P, Q R, S and T, N-2,2-difiuoro-n-propyl-N-p,'y-y dihydroxypropyl-m-chloroaniline, N-2,2difiuor0- n propyl-N-B,' dihydroxypropyl-m-toluidine, N*- 3,3 -difiuoro-n-propyl N-B,' -dihydroxyp1'opylaniline, N-2,2-difluoroethyl-N-fi,' -dihydroxypropylaniline, N 3,3 difluoro-npropy1-N-;3,' -dihydroxypropyl-m-chloroaniline, N -'4,4-dif1uoron amyl-N-Bxy-dihydroxypropyl-m-toluidine, N 2,2 difluoroethyl N d'y-dihydroxypropyl-methylaniline; etc. are prepared.

Compounds having. the formula numbered V are prepared by reacting a compound having the formulaz VIII with 1,1-difiuoro-2-bromoethane or 1,1-difluoro- (CHFZCHzCHaBl), 2,2-difiuoro-n-propylbromide (CI-IxCFzCI-IzBr) 3,3 difluoro-n-butylchloride (CI-IaCFzCHzCHaCl) and 4,4 difiuoro n amylatropine insoluble material-. The benzene layer was? wa'shedwith water and-then the benzenew'as removed by-dis'tillation. Upon distillation under reduced pressure through a 12-" indented column;

66- grams of N 2,;-difiuoroethylaniline, boiling at l 104 c. 106 'C.'/ 19 mm. was obtained. 1

EXAMPLE- V N-2,2 di um-o-n-pmpyz-amzme' 28 grams of aniline, 43 grams of 2,2-difiuoron-propylbromide, grams of sodium bicarbonate and 1 gram of sodium iodide were placed in-an autoclave and heated v24 hours at 170 C. with shaking. The reactionmixture was then cooled, washed-out of the-autoclave withbenzene and filtered: Thebenzene-wasthen removed from the"fi1'trate and the residue containing the de sired reaction productwas distilled under reduced pressure. n-propylaniline boiling at 103 (IL-107 C./ 12 mm. was obtained.

MPL v N-3 ,3-difluoro n-propylaniline By the-use of 43gramsof-3,31-difluoro-n-propylbromide .in. place of 2,2-difluoro n-propylbro-.

midedm Example N- 3',3difluoro-nepropylaniline'boilingat 125 C..-126 C./16 mm. was obtained.

Following theprocedure described in Examples.

m-chloroaniline-B. P. 129-C.-133 C./16 mm.;

ethy1ani1ine,-B. -P. 120 C.-123 C112 mm.;-- N- 2,2edifluoro-n-propylem chloroaniline, B.--P. 115

C./7 mm. etc., are prepared.-

EXAMPLE X N-"3,3-difluoro-n-butylaniline' A mixture of'24 grams of 3,3-difluoro-n-butylr chloride (CH3CF2CH2CH2C1) and 35.3 grams of aniline were heated in a sealed tube at 160 C. for 24 hours. Upon cooling, the tube was opened and the oily solid content was washed out with a 10% aqueous sodium hydroxide solution, yielding anvoilw The aqueous phase of the reaction mix-- ture was extracted with ether, and the ether ex-.

tractuwas combined with the oil. After drying theaethe'r solution over K2003, the ether was re;- moved; and the residue was fractionated under reducedpressure in a small helix-packed column. A;:.54'% ayield 10f" N-3,3-difluoro-n-butylanili'ne boilingsrat 122.-.C.'-123 C./10 mm.,: 11. 29 1.5087, was obtained.

In like manner, N-3,3 -difluoro n-butyl mtoluidine boiling at 135 (l -136 C./l0 mm., 11

examplmareobtained.

EXAMPLE Y z 2815 grams of 4,4,-difluoro-mamylchloride and f 37' grams 'of' aniline "are heated together-'inan Erlenmeyerfiaskpn a steam bath for 36"hours.' The reaction mixture is cooled and made alkaline by'th'eladdition" of 10%" aqueous NaOH: Then the reaction'mixture' is extracted with benzene? and the benzeneextract is distilled under reduced pressure. N-4,4.-difiuoro-n 5 amylaniline' boiling at 101C.-102"C./2"mm; is obtained;

Following the procedure described in Exam? etc., were prepared. l

1,1-difiuoro-3bromopropane appears to be a new compound. pared as described hereinafter.

It was pre- EXAMPLE 2 Preparation of 1,1-diflu0ro-3-bromopropan'e'-W 98 grams of 1,1,3-tribromopropanetwere placed in a 200 cc. round bottomed flask fitted with a still-head and a well-cooled receiving flask. 107 grams of dry 'mercuric'fluoride were then added and the reaction flask was gently heatedwith a free flame until reaction began. The reactionwas then allowed to proceed briskly but not to'ovigorously"(by'cooling-in a bath-of ice water 'or heating, as required) until 'all 'th-reaction product has distilled over atabout C.-'C.' The crude product was then steamdistilled, *dried and fractionated. The main product was1,1-difluoro 3-bromopropane; boiling'point 92 Q' -94- C. Using this procedure" yields of-35-'40'%"'of 'pure 1,1-difluoro 3-bromo'- propane" are obtainedf A small amount of CHzFCHzCHzBr was present in the residue.

1,1,3 J tribromopropane (CHBrrCHECHZBr) likewise appears to be a new compound. It' was prepared as described hereinafter.

I EXAMPLE AA Preparation of- 1,1,3-trz'bromopropane 1000 grams of bromoform and 30 grams of benzoyl peroxide were placed in a 1100 cc. shaking autoclave and ethylene'was passedinto the" autoclave until a pressure of 700 lbs. per square inch was reached. The reaction mixture was then heated at 85" Cifor 15hours following which it was-cooled, removed from the autoclave andfractionated under reduced pressure. Aboutv 600=grams of 1,1,3-tribromopropane boiling at lurid-107+ c. 30 mm. were obtained. --Using the procedure just described or. generally similarly procedures somewhat higher andsomewhat lower yields were obtained. As highas. 700 grams have been obtained. Also 100-150.

grams of bromoform, 20-30 grams of a low boilng liquid and varying amounts of higher boilmg. compounds are recovered.

The azo dye compounds of my invention can be applied to the textile materials named hereinbeforewin the form of an aqueous dispersion.

and are. ordinarily Isa-applied. I To illustrate-the:-

dye compound is finely ground with a dispersing agent such as sodium lignum sulfonate, Turkey red oil, soap, or an oleyl glyceryl sulfate and the resulting mixture is dispersed in water. The dye bath thus prepared is heated to a temperature approximating 45 C.55 C. and the textile material to be dyed is immersed in the dyebath, following which the temperature is gradually raised to 80 C.-90 C. and maintained at this temperature until dyeing is complete, usually one-half to two hours. From time to time throughout the dyeing operation, the material is worked to promote even dyeing. Upon completion of the dyeing operation, the textile material is removed from the dyebath, washed with an aqueous soap solution, rinsed well with water and dried.

The procedure just described is applicable whether the dye compound contains a sulfato group or not. The dye compounds of the invention not containing a sulfato group are practically water-insoluble. Where a sulfato group is present, the water solubility is increased and in such case a greater amount of the dye will go into solution.

Widely varying amounts of dye can be used in the dyeing operation. The amount of dye used can be, for example, to 3% (by weight) of that of the textile material although lesser or greater amounts of dye can be employed.

This application is continuation-in-part of my copending application Serial No. 109,056, filed August 6, 1949. It is also a continuationin-part of my application Serial No. 631,463, filed November 28, 1945, now U. S. Patent 2,516,302. N difiuoroalkylaminobenzene compounds are described and claimed in my application Serial No. 624,943, filed October 26, 1945, now U. S. Patent 2,516,107. Applications Serial Nos. 631,468 and 624,943 were copending with my copending application Serial No. 109,056.

I claim:

1. The azo compounds having the formula:

| l 1 W Z wherein R represents a member selected from the group consisting of a B-suliatoethyl group, a 7- 26 sulfatopropyl group and a sulfated B,v-dihy droxypropyl group, R1 represents a member selected from the group consisting of a 2,2-difluoroethyl group, a 2,2-difluoro-n-propyl group, a 3,3-difiuoro-n-propyl group, a 3,3-difiuoro-nbutyl group and a 4,4-difiuoro-n-amyl group, Z represents a member selected from the group consisting of a hydrogen atom, a bromine atom, a chlorine atom, a methyl group and an ethyl group and W represents a member selected from the group consisting of a H -s OzN-OH3 group and a group.

2. The azo compound having the formula:

CH2CHF2 3. The azo compound having the formula:

CHzOHFZ SOgN-OHS sulfatoethyl sulfatocthyl 5. The azo compound having the formula:

OzN-CzHa C1 6. The azo compound having the formula:

3sulfatocthyl NOW- JOSEPH B. DICKEY.

No references cited. 

1. THE AZO COMPOUNDS HAVING THE FORMULA: 